5-Allyl-4,6-dichloropyrimidine → 5-Allyl-4-chloro-6-(pyridin-2-yl)pyrimidine

HRID 717570Notes

Reaction equation

HRID 717570 reaction equation
[CH2:1]([C:4]1[C:5](Cl)=[N:6][CH:7]=[N:8][C:9]=1[Cl:10])[CH:2]=[CH2:3].C([Sn](CCCC)(CCCC)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=1)CCC>CN(C=O)C>[CH2:1]([C:4]1[C:9]([Cl:10])=[N:8][CH:7]=[N:6][C:5]=1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=1)[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 5192085-Allyl-4,6-dichloropyrimidineHCID 6077842-(Tributylstannyl)pyridine

Product 1

HCID 898144745-Allyl-4-chloro-6-(pyridin-2-yl)pyrimidineYield 40.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

The 5-allyl-4,6-dichloropyrimidine (2 g) and 2-(tributylstannyl) pyridine (6.1 g) were dissolved in dry DMF (1.0 mL). The reaction mixture was degassed with nitrogen for 30 minute and Pd(PPh3)4 (615 mg) was added. The reaction mixture was again degassed with nitrogen for 20 minutes before being irradiated under microwave at 160° C. for 30 minutes. The reaction mixture was cooled to room temperature, filtered through a celite pad and washed with ethyl acetate (2×50 mL). The combined filtrate was washed with water (30 mL) and brine (30 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated. The resulting residue was purified by column chromatography using EtOAc/hexane (0.4:9.6) as eluent to afford 5-allyl-4-chloro-6-(pyridin-2-yl)pyrimidine (1 g) as off white solid. 1H NMR (DMSO-d6): δ 3.80-3.82 (d, 2H), 4.83-4.89 (dd, 1H), 4.90-5.00 (dd, 1H), 5.82-5.88 (m, 1H), 7.53-7.57 (m, 1H), 7.90-8.04 (m, 2H), 8.69-8.71 (d, 1H), 9.0 (s, 1H).

Workup

  1. customThe reaction mixture was degassed with nitrogen for 30 minute
  2. additionPd(PPh3)4 (615 mg) was added
  3. customThe reaction mixture was again degassed with nitrogen for 20 minutes
  4. custombefore being irradiated under microwave at 160° C. for 30 minutes
  5. filtrationfiltered through a celite pad
  6. washwashed with ethyl acetate (2×50 mL)
  7. washThe combined filtrate was washed with water (30 mL) and brine (30 mL)
  8. dry with materialThe organic layer was dried over anhydrous Na2SO4
  9. concentrationconcentrated
  10. customThe resulting residue was purified by column chromatography

Sources & evidence

ORD record
ord-0fb58590fc384f0694af952fb1f4e824
Source dataset
uspto-grants-2015_11
Patent number
US09193725B2

Reaction notes

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